DE2207575B2 - Means for regulating plant growth - Google Patents

Description

/
CH,

CH,

in which X ^{s is} an anion of an inorganic or organic, but not phytotoxic acid and A is a chain of 4 or 5 methylene groups, which is optionally substituted by chlorine or contains a 2 »double bond, or A is the chain

- (CH ₂ J ₄ - NH-

means contains.

30th

The present invention relates to agents for regulating plant growth, which are used as active ingredients Salts containing cyclic nitrogen-containing compounds, and the use of these salts for regulation of plant growth.

It is known that nitrogenous compounds such as chlorcholine chloride (CCC) (J. Biol. Chem. 235,475 [1960] or 1 - (/ J-chloroethyl) -1,1 -dimethylhydrazinium chloride (CMH) (Naturwissenschaften 55, 217 [1968]) or an N-methyl-piperidine salt, which is attached to nitrogen by a lower, optionally halogen-substituted alkyl, alkenyl or aralkyl radical is substituted, for example the N-bromomethyl-N-methyl-piperidine bromide, in a mixture with a nitrogenous fertilizer, especially calcium cyanamide, and a selective herbicide (CH-PS 4 54 926) to use to influence plant growth. These connections intervene in the physiological events of plant growth and can therefore be used as plant growth regulators be used.

One of the typical effects of plant growth regulators is the reduction in length growth. Similarly, germ or flower induction can take place, i. H. influencing the herbal annual rhythms. The formation of side shoots can also be promoted by growth regulators or be inhibited.

Of economic interest, for example, is the prevention of the "storage" of grain in front of the Harvest through growth regulators or the reduction of grass cover on roadsides and on Lawn areas so that frequent mowing can be reduced.

When using the known growth regulators z. B. on cereals where a squat If growth is to be achieved for the formation of the camp, the effect is poor.

45

50

60

CH,

CH.,

in which X is the anion of an inorganic or organic, but not phytotoxic acid, preferably Chloride or bromide, and A is a chain of 4 or 5 methylene groups, optionally through Chlorine is substituted or contains a double bond, or A is the chain

- (CH ₂ J ₄ -NH-

means that numerous plants are suitable for regulating growth, which is particularly evident in expresses a reduction in the growth in length. The effect is better than that of known growth regulators.

The salts can also be used with other crop protection agents, i. H. together with herbicides, insecticides, in particular, however, fungicides can also be used. The application is also advantageous in practice of salts together with fertilizers, especially mixing with urea.

The effect is particularly evident in cereals, e.g. B. wheat, rye, barley, rice and oats, but also with Dicots (e.g. potatoes, tomatoes, vines, cotton) and various ornamental plants such as poinsettias and Hibiscus. The treated plants accordingly have a short stature and generally a stocky one Habit on; a darker leaf color can also be observed.

The effectiveness of the salts is due to the cation, so that the choice of Anton can be arbitrary. Anions However, phytotoxic acids should not be used if solely aimed at influencing the Plant growth and no importance is attached to killing the plants. Suitable acids are for example hydrochloric acid, hydrobromic acid, sulfuric acid, carbonic acid, nitric acid, phosphoric acid, Acetic acid, propionic acid, benzoic acid, sulfuric acid monomethyl or ethyl ester, 2-ethylhexanoic acid, Acrylic acid, maleic, succinic, adipic acid, formic acid, chloroacetic acid, p-toluenesulfonic acid, Benzenesulfonic acid.

The salts can be added to the plants either through the soil, ie through the roots, or by spraying through the leaves. In addition to treating the soil and leaves, the seeds can also be treated. As a result of the relatively high plant tolerance, the application rate can vary considerably, for example up to 15 kg active ingredient / ha. In general, however, doses of 0.01 to 8 kg / ha are to be regarded as sufficient.
The effective salts include:

4-chloro-l, l-dimethylpiperidinium chloride (m.p.

230 ° with decomposition),

3-ChIOr-I ₁ I-dimethyl-piperidinium-chloride (m.p.

245 ° with decomposition),

l, l-dimethyl piperidinium chloride (melting point> 350 °),

1,1-dimethylpiperidinium bromide (mp. 346 ° from Ethanol),

1,1-dimethylpiperidinium iodide (mp. 350 ° below Decomposition),

S ^ -Dehydro-U-dimethyl-piperidinium-chloride

(Mp. 330 ° with decomposition),

3,4-dehydro-1,1-dimethyl-piperidinium bromide

(Fig.p.> 300 °),

3,4-dehydro-l, l-dimethyl piperidinium iodide (m.p.

274-275 ° with decomposition),

1,1-dimethyl-pyrrolidinium-chloride,

1,1-dimethyl-pyrrolidinium bromide (melting point 342 ° from

Ethanol),

1,1-dimethyl-pyrrolidinium chloride, 1,1-dimethyl-pyrrolidinium bromide (melting point 342 ° from

Ethanol),

3,4-dehydro-l, l-dimethyl-pyrrolidinium iodide (m.p.

286 ° with decomposition.

They are all hygroscopic, solid connections with a high, little characteristic Melting point, which normally increases with decreasing water content.

The salts are generally known. In the following, some references are given that the production describe some of these salts:

R. R. R e η s h a w et al., J. Amer. Chem. Soc. 60.745 (1938); ibid. 61,638 (1939),

R. Willstätter, Chem. Ber. 33,365 (1900).

E. Wedekind and R. Oechslen, Chem. Ber. 35, 1076 (1902).

F. Weygand and H. DaηieI, Chem. Ber.94, 1688, (1961).

R. Lukes et al. Vesely, Coll. Czech. Chem.

Commun. 22,638 (1957).

]. v. Braun and W. Teuffert, Chem. Ber.

61, 1092 (1928).

C. M a η η i c h, Archiν Pharm. 272,323 (1934).

G. L. C i a m i c i a η u. M. D e 11 η s t e d t, Chem. Ber. 16.1542 (1883).

M. Saunders and E. H. GοId, J. Amer. Chem. Soc. 88, 3376 (1966).

The salts can be obtained in a very simple way, if you have a tertiary cyclic amine with an alkyl halide or according to the following scheme Reacts dialkyl sulfate in an inert solvent:

_i_ D V

-Γ Κ Λ

'Ν'

CH ₃

■ Ν '

CH ₃

25th

30th

35

45

50

The following examples describe the preparation of some salts by various methods.

example 1

Parts (parts by weight) of 4-chloro-1-methyl-piperidine are dissolved in 150 parts of absolute ether and 40 parts of a 5 n-methyl bromide solution in acetonitrile added dropwise. After 4 hours, the resulting precipitate is filtered off with suction, 22 parts of 4-chloro-1,1-dimethylpiperidinium bromide being obtained with a melting point of 285 ° C (with decomposition).

Example 2

19.3 parts of II-dimethyl-l ^ .e-tetrahydro-pyrazini- _b5 um bromide are dissolved in 50 parts of methanol and 1.5 parts of palladium on carbon in a roll bomb at room temperature under a hydrogen pressure of

55

60 20 atmospheres hydrogenated. The catalyst is then filtered off and evaporated to dryness, 15 parts of 1,1-dimethylhexahydropyridaziniiim bromide having a melting point of 250 ° C. (with decomposition) being obtained.

Example 3

19.4 parts of 1,1-dimethylpiperidinium bromide become dissolved in 60 parts of water and stirred with 40 parts of silver chloride for 30 minutes at room temperature. It is then filtered and the filtrate is evaporated in vacuo. The remaining residue is with Acetone and ether washed and dried. 13.5 parts of 1,1-dimethylpiperidinium chloride are obtained. Fp. over 350 ° C.

The agents according to the invention can be used as solutions, emulsions, suspensions, granulates or dusts be applied. The forms of application depend entirely on the intended use; they should be in ensure a fine distribution of the active substance in each case.

The solution in water can be used to produce directly sprayable solutions. It can but also dispersions in hydrocarbons with boiling points higher than 150 ° C, e.g. tetrahydronaphthalene or alkylated naphthalenes, or organic liquids with boiling points higher than 150 ° C and one or more functional groups, e.g. B. the keto group, the ether group, the ester group or the amide group, this group being a substituent on a hydrocarbon chain or part of a heterocyclic ring can be used as spray liquids.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders) can be prepared by adding water. To produce emulsions, the substances can be used as those or dissolved in a solvent, by means of wetting agents or dispersants, e.g. B. polyethylene oxide addition products be homogenized in water or organic solvents. But it can also look like active substance, emulsifying or dispersing agent and possibly solvents which are suitable for dilution with water.

Dusts can be produced by mixing or grinding together the active substances with one solid carrier, e.g. B. kieselguhr, talc, clay or fertilizers are produced, in the case of granules Mixtures with fertilizers are preferred.

The biological effectiveness of some compounds is demonstrated by the following examples.

Example 4
Effect on wheat

Wheat grains of the »Opal« variety in sown loamy sandy soil. Immediately after sowing, the treatment was carried out at application rates of 3 mg / vessel and 6 mg / vessel, corresponding to 3 and 6 kg / ha. The active ingredients were based on an aqueous solution sprayed the soil surface. In addition to an untreated control vessel, was used as a comparison substance Chlorcholine chloride (CCC) used at the same application rates. The experiment under greenhouse conditions was carried out showed the following result 20 days after the treatment:

Active ingredient

Height (relative) at

Active ingredient concentration

from

3 mg / vial 6 mg / vial

Control (untreated) 100 100

CCC 88 85

CMH 92 86

1,1-dimethyl-3,4-dehydro-85 85 "'piperidinium bromide

In the above experiment it was shown that the active ingredient has a better effect than CCC at a low dose. Even with the other cereals a better effect against CCC, as the following examples showed apparent ι ^r>.

Example 5 Effect on barley

Under the same conditions as in Example 4, the active ingredients were applied to barley of the “Breuns-Wisa” variety tested. The treatment here was, however, with amounts of 1.5 mg / vial, 3 mg / vial and 6 mg / vial carried out at a plant height of 10 cm. After 6 days the following influence was evident in the Growth:

Active ingredient

Height of growth (relative) with active ingredient concentration from

1.5 mg /
vessel

3 mg / vial

6 mg / vial

Example 7
Effect on oats

In the case of oats of the »Flämingskrone« variety, the active ingredients were tested under the same test conditions as tested in Examples 4 and 6. The application rates were 1.5 mg / vessel, 3 mg / vessel and 12 mg / vessel, corresponding to 1.5-12 kg / ha. The following reduction was seen 20 days after treatment the height:

Control (untreated) 100 100 100

CCC 93 91 94

CMH 89 91 87

4-chloro-l, l- 89 89 87

dimethyl piperi-

dinium bromide

1,1-dimethyl-85 79 83

3,4-dehydro-piperi-

dinium bromide

Example 6 Effect on rye

Another experiment was carried out under the same conditions as in Example 4 on rye of the variety "Petkuser" carried out. Amounts of active ingredient were used for the treatment carried out over the ground of 3 mg / vessel, 6 mg / vessel and 12 mg / vessel, corresponding to 3 to 12 kg / ha selected. 20 days after the Treatment, the following result was found.

Active ingredient

Height of growth (relative) with active ingredient concentration of

1.5 mg /
vessel

3 mg /
vessel

12 mg /
vessel

Control (untreated) 100 100 100

CCC 97 94 87

4-chloro-l, l-di- 92 94 87

methyl piperi-

dinium bromide

1,1-dimethyl- 94 92 79

3,4-dehydro-piperi-

dinium bromide

Example 8
Effect on potatoes

Potato plants of the cultivar »Tasso« (semi-early) were also grown at a height of 8 to 15 cm tested. They were also tested at application rates of 8 to 15 cm. They were applied in amounts of 1.5 kg / ha and 6 kg / ha sprayed. After 2 weeks the following result was shown:

Active ingredient

Height (relative) at
Application rates of

1.5 kg / ha 6 kg / ha

Control (untreated) 100 100

CCC 97 93

4-chloro-l, l-dimethyl- 97 89
piperidinium bromide

1,1-dimethyl-3,4-dehydro-86 65
piperidinium bromide

Example 9

Active ingredient

Height of growth (relative) with active ingredient concentration of

3 mg /
vessel

6 mg / vial

12 mg / vial

Control (untreated) 100 100 100

CCC 88 89 88

CMH 88 88 85

1,1-dimethyl- 84 82 84 3,4-dehydropiperidinium bromide

Using the same experimental technique as in Example 4, in an experiment with barley (Breuns-Wisa variety) the

bo effect of 1,1-dimethyl-hexahydropyridazinium bromide in comparison to CCC in application rates of 3 and 12 mg / vessel, corresponding to 3 and 12 kg / ha Use of the active ingredients checked immediately after sowing. Three weeks after treatment

b5 was the height of the barley plants accordingly the following figures are determined. As can be seen from this, it was pyridazinium bromide Clearly superior to the well-known CCC.

Active ingredient

Height (relative) at

Active ingredient concentration

from

.1mg /
(iclalj

12 mg /
CJcIlHi

control

1,1-dimethyl-hydroxahydro-

pyridazinium bromide

100
90

100
82

72

IO

Example 10

In a vegetation experiment in Mitscherlich pots (5 1 content) with wheat (Opal variety) pyridazinium compounds were compared with piperidinium salts. the The wheat plants were treated via the leaf at a height of 25 to 30 cm. After that were the treated plants continued to grow to maturity and then the shortening of the stalk was measured. The shortening of the stalk through the various connections can be seen in the following list.

211

Active ingredient AuI "- Straw lengthc relative Wall- 100 lot 80 (kg / ha) cm 65 Untreated (control) _ 83.7 75 lJ-dimethyl-hexahydro- 0.75 66.7 65 pyridazinium bromide 3 54.3 79 l, l-dimethyl-3,4-dehydro- 0.75 62.4 64 piperidinium chloride 3 54.2 1,1-dimethyl piperidinium 0.75 66.4 chloride 3 53.9

40

Example 11

Cotton plants of the Deltapine variety were grown in Mitscherlich pots (5 liters of content) and sprayed at a height of 15 to 20 cm with the respective active ingredient solutions at rates of conversion of 0.75 kg / ha. The height of growth of the cotton plants at the end of the experiment after 2 months can be seen from the following figures .

Active ingredient Aur Plant height relative Wall 100 lot 90 (kg / ha) cm Untreated (control) _ 44.0 77 1,1-dimethyl-hexahydro- 0.75 39.5 pyridazinium bromide 71 U-dimethylO ^ -dehydro- 0.75 33.9 piperidinium chloride 1,1-dimethyl piperidinium 0.75 31.4 chloride

55

b0

Example 12

Spring wheat of the »Opal« variety, grown in new building trays, was grown at a height of around 12 cm sprayed with aqueous solutions of the active ingredients in amounts equivalent to 3 and 6 kg / ha. 14 days after the

Treatment, the wheat plants had the following height:

kg / ha

Unobstructed (control)
(TC (begiinnl) 3

also 6

1. N dimethyl pyrrolidine! at 3
bromide

Stature relative cm KH) 29.5 88.1 26.0 86.4 25.5 89.8 26.5

Br

24.0 81.4

Π1., (H.,

Example 13

In a vegetation test in Mitscherlich pots with spring wheat of the Opal variety, the plants were sprayed with the aqueous active ingredient solution at a height of 28 to 30 cm. When the plants were in a mature state, the measurements of the length of the stalk gave the following values:

Untreated (control)

1,1-dimethylpyrrolidinium

bromide

k _P / ha Straw lengthc relative cm 100 87.0 90.1 78.4

CH., CH.,

Br

Example 14 Effect on wheat

The active ingredients were tested on spring wheat. On the one hand, the treatment was carried out in advance on the ground and on the other hand as a spray treatment on the leaf.

In the case of soil treatment, amounts of active ingredient of 3.6 and 12 kg / ha were used immediately after the sowing Wheat applied as an aqueous solution to the soil surface, while the leaf spraying at a Height of about 12 cm with application rates of 1.5 3 and 6 kg / ha took place. In this case the Measurement of the treated plants made after 12 days while they were in the pre-treatment 23 days after treatment was performed.

The results are compiled in the attached table and show that the effect is before N-bromomethyl-N-methyl-piperidinium bromide essential borrowed weaker than that of N-dimethyl-piperidinium chloride is.

10

Comparison of the effects of N - Bmmmclhyl - N - methyl - piperidiniiimdiloricl and N-Dinicthyl-piperidiniunuhlorid in wheat

Active ingredient Hoclcnl · leluiiulluni! rcl. St.Hl hclKiiullimtj a rcl. ki: ha LHl 100
72.6
67.6
65.9 ki! Ha 29.6
27.0
26.0
25.5 100
91.2
87.8
86.1 Uncharnished
N-dimethyl
pipcridinium chloride 3
6th
12th 29.6
21.5
20.0
19.5 1.5
3
6th / \ 96.3
94.6
91.2 28.0
27.5
27.5 94.6
92.9
92.9 ι 1
N Br 3
6th
12th 28.5
28.0
27.0 1.5
3
6th

CH,

CH ₁ Br

Example 15

Grains (wheat, barley, rye and oats) were placed in glass bowls in a loamy sandy soil sown. Immediately after sowing, the treatment was carried out at application rates of 3 mg and ^ mg / active ingredient / container, corresponding to 3 and 12 kg / ha. The active ingredients were sprayed onto the surface of the soil in an aqueous solution. In addition to untreated controls were N-dimethylpiperidinium chloride and N-methyl-N-isopropylpiperidinium bromide at the same Application rates used. The experiment, carried out under greenhouse conditions, showed 18 days the following result after the treatment:

Active ingredient

Wiichshrihe (relative) at

Summer wheat

Summer summer

Barley rye

lafer

Untreated Cl 3
12th KK) 100 100 100 O 67
61 94
82 93
88 99
90

CH., CH.,

Br

CH.,

CH ₃ CH

3 102 99 103 99 12th 98 97 95 99

CH.,

Claims (1)

Claim: Means for regulating plant growth based on salts of cyclic nitrogenous Compounds, characterized in that they are a salt of the general formula It was found that salts of the general formula